US20130030097A1 - Article, in particular a pneumatic tyre, having an external rubber mixture comprising a lanthanide salt - Google Patents

Article, in particular a pneumatic tyre, having an external rubber mixture comprising a lanthanide salt Download PDF

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US20130030097A1
US20130030097A1 US13/516,876 US201013516876A US2013030097A1 US 20130030097 A1 US20130030097 A1 US 20130030097A1 US 201013516876 A US201013516876 A US 201013516876A US 2013030097 A1 US2013030097 A1 US 2013030097A1
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article according
phr
antioxidant
rubber
mixtures
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US13/516,876
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Nathalie Salgues
Jean-Luc Cabioch
Kazumi Makiuchi
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Compagnie Generale des Etablissements Michelin SCA
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Michelin Recherche et Technique SA Switzerland
Compagnie Generale des Etablissements Michelin SCA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the field of the present invention is that of finished articles made of rubber, in particular vehicle tyres, and mixtures or profiled elements made of rubber used in the manufacture of such articles or tyres.
  • the present invention relates more particularly to antidegradant agents used to protect these rubber mixtures against ageing due to oxidation when they are in contact with air.
  • antioxidants including in particular p-phenylenediamine (“PPD” or “PPDA”) derivatives, such as, for example, N-isopropyl-N′-phenyl-p-phenylenediamine (“I-PPD”) or N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylene-diamine (“6-PPD”), or quinoline derivatives (“TMQ”), simultaneously excellent antioxidants and antiozonants (see, for example, Patent Applications WO 2004/033548, WO 2005/063510 and WO 2005/133666).
  • I-PPD N-isopropyl-N′-phenyl-p-phenylenediamine
  • 6-PPD N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylene-diamine
  • TMQ quinoline derivatives
  • antioxidant reservoirs although effective, however exhibits the disadvantage of having to modify the internal structure of the tyres and consequently in particular of making it more complex and more expensive to manufacture them.
  • a first subject-matter of the invention is an article comprising at least an external mixture made of rubber, the said external mixture comprising a rubber composition based on at least a diene elastomer, a reinforcing filler, a crosslinking system, between 0.2 and 10 phr of an antioxidant and between 0.2 and 10 phr of lanthanide acetylacetonate.
  • the longevity of rubber vulcanisates can thus be improved, in particular that of tyres, which may be subjected, as is known, to particularly severe running conditions, in particular under a humid and corrosive atmosphere.
  • the present invention particularly relates to tyres intended to equip passenger motor vehicles, SUV (Sport Utility Vehicle) vehicles, two-wheel vehicles (in particular bicycles or motorcycles), aircraft, as well as industrial vehicles chosen from vans, heavy-duty vehicles—that is to say, underground, bus, heavy road transport vehicles (lorries, tractors, trailers) or off-road vehicles, such as agricultural vehicles or earth moving equipment—or other transportation or handling vehicles.
  • SUV Sport Utility Vehicle
  • two-wheel vehicles in particular bicycles or motorcycles
  • industrial vehicles chosen from vans
  • heavy-duty vehicles that is to say, underground, bus, heavy road transport vehicles (lorries, tractors, trailers) or off-road vehicles, such as agricultural vehicles or earth moving equipment—or other transportation or handling vehicles.
  • the rubber compositions are characterized, before and after curing, as indicated below.
  • the Mooney plasticity measurement is carried out according to the following principle: the composition in the raw state (i.e., before curing) is moulded in a cylindrical chamber heated to 100° C. After preheating for one minute, the rotor rotates within the test specimen at 2 revolutions/minute and the working torque for maintaining this movement is measured after rotating for 4 minutes.
  • any interval of values denoted by the expression “between a and b” represents the range of values greater than “a” and less than “b” (that is to say, limits a and b excluded), whereas any interval of values denoted by the expression “from a to b” means the range of values extending from “a” up to “b” (that is say, including the strict limits a and b).
  • the rubber article, in particular tyre, of the invention thus comprises at least an external rubber mixture comprising a rubber composition based (i.e., comprising the mixture or the reaction product) on at least a diene elastomer, a reinforcing filler, a crosslinking system and between 0.2 and 10 phr of an antioxidant; in addition, it has the novel and essential characteristic of comprising between 0.2 and 10 phr of a lanthanide acetylacetonate.
  • iene (or indiscriminately rubber) elastomer is understood to mean, in a known way, an elastomer resulting at least in part (i.e., a homopolymer or a copolymer) from diene monomers (monomers bearing two carbon-carbon double bonds which may or may not be conjugated).
  • Diene elastomers can be classified in a known way into two categories: those said to be “essentially unsaturated” and those said to be “essentially saturated”.
  • the term “essentially unsaturated” diene elastomer is understood here to mean a diene elastomer resulting at least in part from conjugated diene monomers having a level of units of diene origin (conjugated dienes) which is greater than 15% (mol %).
  • diene elastomers such as butyl rubbers or copolymers of dienes and of a-olefins of EPDM type do not come within the preceding definition and can in particular be described as “essentially saturated” diene elastomers (low or very low level of units of diene origin, always less than 15%).
  • the term “highly unsaturated” diene elastomer is understood to mean in particular a diene elastomer having a level of units of diene origin (conjugated dienes) which is greater than 50%.
  • diene elastomer capable of being employed in the compositions in accordance with the invention is understood more particularly to mean:
  • diene elastomer any type of diene elastomer
  • a person skilled in the art of tyres will understand that the present invention is firstly employed with essentially unsaturated diene elastomers, in particular of the type (a) or (b) above.
  • the diene elastomer is chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, isoprene copolymers and the mixtures of these elastomers.
  • Such copolymers are more preferably chosen from the group consisting of butadiene/styrene copolymers (SBR), whether the latter are prepared by emulsion polymerization (ESBR) or in solution (SSBR), isoprene/butadiene copolymers (BIR), isoprene/styrene copolymers (SIR) and isoprene/butadiene/styrene copolymers (SBIR).
  • SBR butadiene/styrene copolymers
  • BIR isoprene/butadiene copolymers
  • SIR isoprene/styrene copolymers
  • SBIR isoprene/butadiene/styrene copolymers
  • the elastomers can, for example, be block, random, sequential or microsequential elastomers and can be prepared in dispersion or in solution; they can be coupled and/or star-branched or also functionalized with a coupling and/or star-branching or functionalization agent.
  • a coupling and/or star-branching or functionalization agent for coupling with carbon black, mention may be made, for example, of functional groups comprising a C—Sn bond or of aminated functional groups, such as benzophenone, for example;
  • a reinforcing inorganic filler such as silica, mention may be made, for example, of silanol or polysiloxane functional groups having a silanol end (such as described, for example, in U.S. Pat. No.
  • polybutadienes in particular those having a content (molar %) of 1,2-units of between 4% and 80% or those having a content (molar %) of cis-1,4-units of greater than 80%
  • polyisoprenes in particular those having a Tg (glass transition temperature, measured according to Standard ASTM D3418) of between 0° C. and ⁇ 70° C. and more particularly between ⁇ 10° C.
  • styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (molar %) of 1,2-bonds of the butadiene part of between 4% and 75% and a content (molar %) of trans-1,4-bonds of between 10% and 80%, butadiene/isoprene copolymers, in particular those having an isoprene content of between 5% and 90% by weight and a Tg of ⁇ 40° C. to ⁇ 80° C., or isoprene/styrene copolymers, in particular those having a styrene content of between 5% and 50% by weight and a Tg of between ⁇ 25° C.
  • butadiene/styrene/isoprene copolymers those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60% by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly of between 20% and 40%, a content (molar %) of 1,2-units of the butadiene part of between 4% and 85%, a content (molar %) of trans-1,4-units of the butadiene part of between 6% and 80%, a content (molar %) of 1,2- plus 3,4-units of the isoprene part of between 5% and 70% and a content (molar %) of trans-1,4-units of the isoprene part of between 10% and 50%, and more generally any butadiene/styrene/isoprene copolymer having a T
  • the predominant diene elastomer by weight is an SBR, whether an SBR prepared in emulsion (“ESBR”) or an SBR prepared in solution (“SSBR”), or an SBR/BR, SBR/NR (or SBR/IR), BR/NR (or BR/IR) or also SBR/BR/NR (or SBR/BR/IR) blend (mixture).
  • SBR SBR prepared in emulsion
  • SSBR SBR prepared in solution
  • SBR/BR SBR/NR
  • BR/NR or BR/IR
  • SBR/BR/IR SBR/NR
  • SBR/BR/IR SBR/BR/IR
  • an SBR (ESBR or SSBR) elastomer use is made in particular of an SBR having a moderate styrene content, for example of between 20% and 35% by weight, or a high styrene content, for example from 35 to 45%, a content of vinyl bonds of the butadiene part of between 15% and 70%, a content (molar %) of trans-1,4-bonds of between 15% and 75% and a Tg of between -10° C. and ⁇ 55° C.; such an SBR can advantageously be used as a mixture with a BR preferably having more than 90% (molar %) of cis-1,4-bonds.
  • the predominant diene elastomer by weight is an isoprene elastomer. This is the case in particular when the rubber compositions described are intended to constitute, in the tyres, treads (in particular for industrial vehicles) or sidewalls.
  • isoprene elastomer is understood to mean, in a known way, an isoprene homopolymer or copolymer, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), the various copolymers of isoprene and the mixtures of these elastomers.
  • NR natural rubber
  • IR synthetic polyisoprenes
  • isoprene copolymers of isobutene/isoprene copolymers (butyl rubber—IIR), isoprene/styrene copolymers (SIR), isoprene/butadiene copolymers (BIR) or isoprene/butadiene/styrene copolymers (SBIR).
  • IIR isobutene/isoprene copolymers
  • SIR isoprene/styrene copolymers
  • BIR isoprene/butadiene copolymers
  • SBIR isoprene/butadiene/styrene copolymers
  • This isoprene elastomer is preferably natural rubber or a synthetic cis-1,4-polyisoprene; use is preferably made, among these synthetic polyisoprenes, of the polyisoprenes having a level (molar %) of cis-1,4-bonds of greater than 90%, more preferably still of greater than 98%.
  • the rubber composition in particular when it is intended for a tyre sidewall or for an airtight layer of a tubeless tyre (or other air-impermeable component), can comprise at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer or one butyl rubber (optionally chlorinated or brominated), whether these copolymers are used alone or as a mixture with highly unsaturated diene elastomers as mentioned above, in particular NR or IR, BR or SBR.
  • the rubber composition comprises a blend of a (one or more) “high Tg” diene elastomer exhibiting a Tg of between ⁇ 70° C. and 0° C. and of a (one or more) “low Tg” diene elastomer of between ⁇ 110° C. and ⁇ 80° C., more preferably between ⁇ 105° C. and ⁇ 90° C.
  • the high Tg elastomer is preferably chosen from the group consisting of S-SBRs, E-SBRs, natural rubber, synthetic polyisoprenes (exhibiting a level (molar %) of cis-1,4-structures preferably of greater than 95%), BIRs, SIRs, SBIRs and the mixtures of these elastomers.
  • the low Tg elastomer preferably comprises butadiene units according to a level (molar %) at least equal to 70%; it preferably consists of a polybutadiene (BR) exhibiting a level (molar %) of cis-1,4-structures of greater than 90%.
  • the rubber composition of the invention can comprise just one or several diene elastomers, it being possible for this diene elastomer or these diene elastomers in addition to be used in combination with any type of synthetic elastomer other than a diene elastomer, indeed even with polymers other than elastomers, for example thermoplastic polymers.
  • composition of the invention comprises any type of “reinforcing” filler known for its capabilities of reinforcing a rubber composition which can be used for the manufacture of tyres, for example an organic filler, such as carbon black, a reinforcing inorganic filler, such as silica, with which a coupling agent is combined in a known way, or a mixture of these two types of filler.
  • an organic filler such as carbon black
  • a reinforcing inorganic filler such as silica
  • Such a reinforcing filler typically consists of nanoparticles, the mean size (by weight) of which is less than a micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.
  • the level of total reinforcing filler (in particular of silica or of carbon black or a mixture of silica and carbon black) is between 30 and 150 phr. Above 150 phr, there exists a risk of increase in the hysteresis and thus in the rolling resistance of the tyres. For this reason, the level of total reinforcing filler is more preferably comprised within a range from 40 to 120 phr.
  • tyre tread use is made of 40 to 150 phr, in particular of 50 to 120 phr, of carbon black, of silica, or of a mixture of silica and carbon black.
  • All carbon blacks are suitable as carbon blacks. Mention will more particularly be made, among the latter, of the reinforcing carbon blacks of the 100, 200 or 300 series, or the blacks of the 500, 600 or 700 series (ASTM grades), such as, for example, the N115, N134, N234, N326, N330, N339, N347, N375, N550, N683 or N772 blacks.
  • the carbon blacks might, for example, be already incorporated in the diene, in particular isoprene, elastomer in the form of a masterbatch (see, for example, Applications WO 97/36724 or WO 99/16600).
  • filler should be understood here as meaning any inorganic or mineral filler, whatever its colour and its origin (natural or synthetic), also known as “white filler”, “clear filler” or even “non-black filler” in contrast to carbon black, capable of reinforcing by itself, without means other than an intermediate coupling agent, a rubber composition intended for the manufacture of tyres, in other words capable of replacing, in its reinforcing role, a conventional tyre-grade carbon black; such a filler is generally characterized, in a known way, by the presence of hydroxyl (—OH) groups at its surface.
  • —OH hydroxyl
  • Mineral fillers of the siliceous type are suitable in particular as reinforcing inorganic fillers.
  • the silica used can be any reinforcing silica known to a person skilled in the art, in particular any precipitated or pyrogenic silica exhibiting a BET surface and a CTAB specific surface both of less than 450 m 2 /g, preferably from 30 to 400 m 2 /g, in particular between 60 and 300 m 2 /g.
  • HDS highly dispersible precipitated silicas
  • an at least bifunctional coupling agent intended to provide a satisfactory connection, of chemical and/or physical nature, between the inorganic filler (surface of its particles) and the diene elastomer.
  • Use is made, in particular, of at least bifunctional organosilanes or polyorganosiloxanes.
  • silane polysulphides referred to as “symmetrical” or “asymmetrical” depending on their specific structure, as described, for example, in Applications WO 03/002648 (or US 2005/016651) and WO 03/002649 (or US 2005/016650).
  • the mean value of the “x” symbols is a fractional number preferably of between 2 and 5, more preferably approximately 4.
  • silane polysulphides of bis((C 1 -C 4 )alkoxyl(C 1 -C 4 ) alkylsilyl(C 1 -C 4 )alkyl) polysulphides (in particular disulphides, trisulphides or tetrasulphides), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl)polysulphides.
  • TESPT bis(3-triethoxysilylpropyl)tetrasulphide
  • TESPD bis(triethoxysilylpropyl) disulphide
  • silane sulphides for example, of the silanes carrying at least one thiol (—SH) functional group (“mercaptosilanes”) and/or at least one masked thiol functional group, such as described, for example, in Patents or Patent Applications U.S. Pat. No. 6,849,754, WO 99/09036, WO 2006/023815 and WO 2007/098080.
  • thiol (—SH) functional group mercaptosilanes
  • masked thiol functional group such as described, for example, in Patents or Patent Applications U.S. Pat. No. 6,849,754, WO 99/09036, WO 2006/023815 and WO 2007/098080.
  • the content of coupling agent is preferably between 2 and 15 phr, more preferably between 3 and 12 phr.
  • a reinforcing filler of another nature, in particular organic nature, such as carbon black might be used as filler equivalent to the reinforcing inorganic filler described in the present section, provided that this reinforcing filler is covered with an inorganic layer, such as silica, or else comprises, at its surface, functional sites, in particular hydroxyls, requiring the use of a coupling agent in order to form the connection between the filler and the elastomer.
  • an inorganic layer such as silica
  • silica or else comprises, at its surface, functional sites, in particular hydroxyls, requiring the use of a coupling agent in order to form the connection between the filler and the elastomer.
  • carbon blacks for tyres such as described, for example, in the patent documents WO 96/37547 and WO 99/28380.
  • a reinforcing inorganic filler in particular silica
  • a reinforcing inorganic filler at a level within a range from 70 to 120 phr, to which reinforcing inorganic filler can advantageously be added carbon black at a minor level at most equal to 15 phr, in particular within a range from 1 to 10 phr.
  • the crosslinking system is preferably a vulcanisation system, that is to say a system based on sulphur (or on a sulphur-donating agent) and on a primary vulcanisation accelerator.
  • a vulcanisation activators or secondary accelerators such as zinc oxide, stearic acid or equivalent compounds, or guanidine derivatives (in particular diphenylguanidine), incorporated during the first non-productive phase and/or during the productive phase, as described subsequently, are additional to this base vulcanisation system.
  • the sulphur is used at a preferable level of between 0.5 and 12 phr, in particular between 1 and 10 phr.
  • the primary vulcanisation accelerator is used at a preferable level of between 0.5 and 10 phr, more preferably of between 0.5 and 5.0 phr.
  • Use may be made, as (primary or secondary) accelerator, of any compound capable of acting as accelerator for the vulcanisation of diene elastomers in the presence of sulphur, in particular accelerators of the type of the thiazoles and their derivatives, or accelerators of the types of zinc dithiocarbamates or thiurams.
  • accelerators are, for example, chosen from the group consisting of 2-mercaptobenzothiazyl disulphide (abbreviated to “MBTS”), tetrabenzylthiuram disulphide (“TBZTD”), N-cyclohexyl-2-benzothiazolesulphenamide (“CBS”), N,N-dicyclohexyl-2-benzothiazolesulphenamide (“DCBS”), N-(tert-butyl)-2-benzothiazolesulphenamide (“TBBS”), N-(tert-butyl)-2-benzothiazolesulphenimide (“TBSI”), zinc dibenzyldithiocarbamate (“ZBEC”) and the mixtures of these compounds.
  • MBTS 2-mercaptobenzothiazyl disulphide
  • TBZTD tetrabenzylthiuram disulphide
  • CBS C, N,N-dicyclohexyl-2-benzothiazolesulphenamide
  • DCBS N-(
  • composition of the invention has the characteristic of comprising between 0.2 and 10 phr of an antioxidant, preferably between 0.3 and 6 phr and more preferably within a range from 0.5 to 4 phr of such an antioxidant.
  • the antioxidant used in the composition of the invention is any antioxidant known to be effective in preventing ageing of rubber vulcanisates attributable to the action of the oxygen.
  • PPD para-phenylenediamine
  • PPDA substituted para-phenylenediamines
  • N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine betterer known under the abbreviated term “6-PPD”
  • N-isopropyl-N′-phenyl-p-phenylenediamine abbreviated to
  • I-PPD phenyl-cyclohexyl-p-phenylenediamine, N,N′-di(1,4-dimethylpentyl)-p-phenylene-diamine, N,N′-diaryl-p-phenylenediamine (“DTPD”), diaryl-p-phenylenediamine (“DAPD”), 2,4,6-tris[N-(1,4-dimethylpentyl)-p-phenylenediamino]-1,3,5-triazine, and the mixtures of such diamines.
  • TMQ derivatives of quinoline
  • TMQ 1,2-dihydro-2,2,4-trimethylquinoline and 6-ethoxy-1,2-dihydro-2,2,4- trimethylquinoline.
  • substituted diphenylamines or triphenylamines such as described, for example, in Applications WO 2007/121936 and WO 2008/055683, in particular 4,4′ -bis(isopropylamino)triphenylamine, 4,4′-bis(1,3-dimethylbutyl-amino)triphenylamine or 4,4′ -bis(1,4-dimethylpentylamino)triphenylamine.
  • dialkyl thiodipropionates or also of phenolic antioxidants, in particular of the family of the 2,2′-methylenebis[4-(C 1 -C 10 )alkyl-6-(C 1 -C 12 )alkyl-phenols], such as described in particular in the abovementioned Application WO 99/02590.
  • antioxidant can denote both a single antioxidant compound or a mixture of several antioxidant compounds.
  • the antioxidant is chosen from the group consisting of substituted p-phenylene-diamines, substituted diphenylamines, substituted triphenylamines, quinoline derivatives and the mixtures of such compounds; more preferably still, the antioxidant is chosen from the group consisting of substituted p-phenylenediamines and the mixtures of such diamines.
  • composition of the external mixture comprises between 0.2 and 10 phr of lanthanide acetylacetonate.
  • the said level of lanthanide acetylacetonate is preferably between 0.3 and 6 phr, more preferably still within a range from 0.5 to 4.0 phr.
  • lanthanide is reserved for the metals, referred to as “rare earth metals”, the atomic number of which varies from 57 (lanthanum) to 71 (lutetium).
  • the lanthanide is chosen from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, erbium and the mixtures of these rare earth metals. Use is more preferably made of cerium, samarium or neodymium, in particular neodymium.
  • lanthanide salts have been used essentially to date as catalysts for the polymerization of polymers or elastomers, such as dienes (see, by way of examples, U.S. Pat. No. 3,803,053, U.S. Pat. No. 5,484,897, U.S. Pat. No. 5,858,903, U.S. Pat. No. 5,914,377 or U.S. Pat. No. 6,800,705). They have also been described as promoters of metal/rubber adhesion in internal mixtures for the calendering of metal reinforcers (see abovementioned Application WO 2005/113666).
  • the rubber compositions can also comprise all or a portion of the additives generally used in rubber compositions intended to constitute external mixtures for finished articles made of rubber, such as tyres, such as, for example, plasticizing agents or extending oils, whether the latter are aromatic or nonaromatic in nature, in particular very slightly aromatic or nonaromatic oils (e.g., paraffinic oils, or naphthenic oils which are hydrogenated, MES oils or TDAE oils), vegetable oils, ether plasticizers, ester plasticizers (for example, glycerol trioleates), fillers other than those mentioned above, for example lamellar fillers, plasticizing hydrocarbon resins exhibiting a high Tg, preferably of greater than 30° C., such as described, for example, in Applications WO 2005/087859, WO 2006/061064 and WO 2007/017060, other antidegradant or antiageing agents, such as, for example, antiozonants, vulcanisation accelerators, activators or retarders, methylene acceptors
  • plasticizing hydrocarbon resins can be chosen in particular from the group consisting of cyclopentadiene homopolymer or copolymer resins, dicyclopentadiene homopolymer or copolymer resins, terpene homopolymer or copolymer resins, terpene-phenol homopolymer or copolymer resins, C 5 fraction homopolymer or copolymer resins, C 9 fraction homopolymer or copolymer resins, a-methylstyrene homopolymer or copolymer resins and the mixtures of these resins.
  • the rubber compositions can also comprise coupling activators, when a coupling agent is used, agents for covering the inorganic filler when an inorganic filler is used, or more generally processing aids capable, in a known way, by virtue of an improvement in the dispersion of the filler in the rubber matrix and of a lowering in the viscosity of the compositions, of improving their property of processing in the raw state.
  • hydroxysilanes or hydrolysable silanes such as hydroxysilanes or alkylalkoxysilanes, in particular alkyltriethoxysilanes, such as, for example, (1-octyl)triethoxysilane, polyols (for example, diols or triols), polyethers (for example, polyethylene glycols), primary, secondary or tertiary amines (for example trialkanolamines) or hydroxylated or hydrolysable polyorganosiloxanes (for example, ⁇ , ⁇ -dihydroxypolyorganosilanes, in particular ⁇ , ⁇ -dihydroxypolydimethylsiloxanes).
  • hydroxysilanes or hydrolysable silanes such as hydroxysilanes or alkylalkoxysilanes, in particular alkyltriethoxysilanes, such as, for example, (1-octyl)triethoxysilane,
  • compositions are manufactured in appropriate mixers using two successive preparation phases well known to a person skilled in the art: a first phase of thermomechanical working or kneading (“non-productive” phase) at high temperature, up to a maximum temperature of between 110° C. and 190° C., preferably between 130° C. and 180° C., followed by a second phase of mechanical working (“productive” phase) up to a lower temperature, typically of less than 110° C., finishing phase during which the crosslinking system is incorporated.
  • a first phase of thermomechanical working or kneading at high temperature, up to a maximum temperature of between 110° C. and 190° C., preferably between 130° C. and 180° C.
  • a second phase of mechanical working (“productive” phase) up to a lower temperature, typically of less than 110° C., finishing phase during which the crosslinking system is incorporated.
  • the non-productive phase is carried out in a single thermomechanical stage of a few minutes (for example, between 2 and 10 min) during which all the base constituents necessary and other additives, with the exception of the crosslinking or vulcanisation system, are introduced into an appropriate mixer, such as a normal internal mixer. After cooling the mixture thus obtained, the vulcanisation system is then incorporated in an external mixer, such as an open mill, maintained at low temperature (for example, between 30° C. and 100° C.). The combined mixture is then mixed (productive phase) for a few minutes (for example, between 5 and 15 min).
  • lanthanide acetylacetonate is introduced during the non-productive phase, at the same time as the antioxidant.
  • the invention also applies to the case where all or only a fraction of this acetylacetonate is introduced during the productive phase.
  • the final composition thus obtained can subsequently be calendered, for example in the form of a sheet, or else extruded, for example to form an external rubber profiled element for a tyre, such as, for example, a tread.
  • the vulcanisation (or curing) can subsequently be carried out in a known way at a temperature generally of between 130° C. and 200° C., preferably under pressure, for a sufficient time which can vary, for example, between 5 and 90 min, depending in particular on the curing temperature, the vulcanisation system adopted and the vulcanisation kinetics of the composition under consideration.
  • the invention relates to the rubber articles, in particular the tyres, both in the “raw” state (i.e., before curing) and in the “cured” or vulcanised state (i.e., after vulcanisation).
  • the rubber composition described above can preferably be used for the manufacture of any external mixture intended for a tyre for a motor vehicle.
  • “External” or “exterior” mixture is understood here to mean any part made of rubber of the tyre (more generally of a rubber article) which opens onto the outside of the said tyre, in other words which is in contact with the air or with an inflation gas; mention may be made, as examples, of the tread, sidewalls or airtight layer of the tyre.
  • Internal or “interior” mixture is understood to mean, in contrast, any part made of rubber of the tyre (more generally of a rubber article) which does not open onto the outside of the tyre, which is not in contact with the air or an inflation gas, in other words which is thus situated in the actual inside of the internal structure of the tyre; mention may be made, as examples, of the mixtures for the calendering of metal reinforcers present in the carcass reinforcement or the crown reinforcement of the tyre.
  • the single appended figure represents, highly diagrammatically, a radial cross section of a tyre with radial carcass reinforcement in accordance with the invention, for example intended for a heavy duty vehicle or for a passenger vehicle in this general representation.
  • the tyre ( 1 ) represented diagrammatically comprises a crown region ( 2 ) comprising a tread ( 3 ) (for simplification, comprising a very simple tread pattern) intended to come into contact with the road and two nonextendable beads ( 4 ) in which a carcass reinforcement ( 6 ) is anchored.
  • the crown ( 2 ), joined to the said beads ( 4 ) via two sidewalls ( 5 ), is, in a way known per se, reinforced by a crown reinforcement or “belt” ( 7 ) at least partially made of metal and radially external with respect to the carcass reinforcement ( 6 ) passing through this crown region ( 2 ), this belt ( 7 ) being, for example, composed of at least two superimposed crossed plies reinforced by metal cords.
  • the carcass reinforcement ( 6 ) is anchored here in each bead ( 4 ) by winding around two bead threads ( 4 a , 4 b ), the turn-up ( 6 a , 6 b ) of this reinforcement ( 6 ) being, for example, positioned toward the outside of the tyre ( 1 ), which is here represented fitted to its wheel rim ( 9 ).
  • the carcass reinforcement ( 6 ) is composed of at least one ply reinforced by textile or metal radial cords, that is to say that these cords are positioned virtually parallel to one another and extend from one bead to the other, so as to form an angle of between 80° and 90° with the median circumferential plane (plane perpendicular to the axis of rotation of the tyre which is situated at mid distance from the two beads 4 and passes through the middle of the crown reinforcement ( 7 ).
  • this tyre ( 1 ) additionally comprises, in a known way, an airtight layer ( 10 ), which defines the radially internal face of the tyre and which is intended to protect the carcass ply from the diffusion of air or another inflation gas originating from the space ( 11 ) interior to the tyre casing.
  • an airtight layer ( 10 ) which defines the radially internal face of the tyre and which is intended to protect the carcass ply from the diffusion of air or another inflation gas originating from the space ( 11 ) interior to the tyre casing.
  • the tyre in accordance with the invention has the essential characteristic of comprising, in its structure, at least an external mixture according to the invention, constituting, for example, all or part of the tread ( 3 ), or of the sidewalls ( 5 ), or of the airtight layer ( 10 ).
  • control compositions (C-1 and C-3) essentially comprise, in a known way, in addition to the elastomer and the reinforcing filler (silica and carbon black), a silane coupling agent, a plasticizing system composed of an oil and of a thermoplastic hydrocarbon resin, an antioxidant, zinc oxide, stearic acid, guanidine derivative, sulphur and sulphenamide accelerator.
  • silane coupling agent silane coupling agent
  • plasticizing system composed of an oil and of a thermoplastic hydrocarbon resin
  • an antioxidant zinc oxide
  • stearic acid stearic acid
  • guanidine derivative sulphur and sulphenamide accelerator
  • compositions according to the invention differ from the two previous compositions (respectively C-1 and C-3) only in the additional presence alone of 2.0 phr of lanthanide acetylacetonate compound (neodymium).
  • compositions were manufactured in the following way: the reinforcing filler (silica and carbon black), the diene elastomer (SBR or SBR/BR blend), an antioxidant, the various other plasticizers, if appropriate, the acetylacetonate, and also the various other ingredients, with the exception of the vulcanisation system, were successively introduced into an internal mixer, the initial vessel temperature of which was approximately 60° C.; the mixer was thus approximately 70% filled (% by volume). Thermomechanical working (non-productive phase) was then carried out in a stage of approximately 2 to 4 min, until a maximum “dropping” temperature of 165° C. was achieved. The mixture thus obtained was recovered and cooled and then sulphur and an accelerator of sulphenamide type were incorporated on an external mixer (homofinisher) at 30° C., the combined mixture being mixed (productive phase) for several minutes.
  • the reinforcing filler silicon and carbon black
  • SBR or SBR/BR blend diene elastomer
  • compositions thus obtained are subsequently either calendered in the form of sheets (thickness of 2 to 3 mm) for the measurement of their physical or mechanical properties, on the one hand, and for carrying out the ageing tests, on the other hand.
  • compositions C-2 and C-4 have been listed in the appended Table 2.
  • the two compositions in accordance with the invention have an advantageously reduced Mooney viscosity, an indicator of an improved processability.
  • the four compositions After curing (15 min at 160° C.), the four compositions have equivalent properties, apart from an elongation at break which is advantageously greater in the presence of the acetylacetonate (compositions C-2 and C-4 in accordance with the invention).
  • the rubber blocks After curing the compositions, the rubber blocks are placed in an oven at a temperature of 55° C., under a relative humidity of 95%, for one to several weeks, in order to compare the kinetics of reduction in the level of antioxidant of the compositions during this accelerated ageing.
  • the level of antioxidant was measured by a known HPLC (high performance liquid chromatography) technique, on the one hand in the initial state, on non-aged test specimens, that is to say directly on exiting from the curing, and, on the other hand, after ageing for one to six weeks.
  • the results obtained are given in the appended Table 3.
  • the level of antioxidant in the compositions is expressed in relative units, the base 100 being selected for each control composition in the initial state (i.e., after exiting from the curing).
  • the elongation at break properties are expressed in relative units, the base 100 being selected for each control composition in the initial state (i.e., after exiting from the curing).
  • the base 100 being selected for each control composition in the initial state (i.e., after exiting from the curing).
  • Table 4 it is clearly found that the presence of the lanthanide acetylacetonate already makes it possible, immediately after curing (initial state), to substantially (approximately 14%) reduce the loss in elongation at break of the composition.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
US13/516,876 2009-12-22 2010-12-14 Article, in particular a pneumatic tyre, having an external rubber mixture comprising a lanthanide salt Abandoned US20130030097A1 (en)

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FR0959346A FR2954332B1 (fr) 2009-12-22 2009-12-22 Article notamment pneumatique avec melange de caoutchouc externe comportant un sel de lanthanide
FR0959346 2009-12-22
PCT/EP2010/069636 WO2011076619A1 (fr) 2009-12-22 2010-12-14 Article notamment pneumatique avec melange de caoutchouc externe comportant un sel de lanthanide

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JPWO2016039003A1 (ja) * 2014-09-12 2017-06-22 宇部興産株式会社 ゴム組成物
FR3058149A1 (fr) * 2016-10-31 2018-05-04 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant une charge renforcante specifique
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US20150246581A1 (en) * 2012-10-30 2015-09-03 Compagnie Generale Des Etablissements Michelin Cord rubberized in situ comprising a composition comprising a styrene-butadiene copolymer
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US20160002371A1 (en) * 2013-02-25 2016-01-07 The Yokohama Rubber Co., Ltd. Rubber Composition for Tires, and Pneumatic Tire Using Same
US9593181B2 (en) * 2013-02-25 2017-03-14 The Yokohama Rubber Co., Ltd. Rubber composition for tires, and pneumatic tire using same
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US11230636B2 (en) * 2017-02-20 2022-01-25 Compagnie Generale Des Etablissements Michelin Rubber composition having improved properties in the raw state and in the cooked state
CN113015630A (zh) * 2018-11-15 2021-06-22 米其林集团总公司 设置有胎面的轮胎

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EP2516177A1 (fr) 2012-10-31
CN102666131B (zh) 2015-09-16
EA201290563A1 (ru) 2013-05-30
IN2012DN04929A (enrdf_load_stackoverflow) 2015-09-25
CN102666131A (zh) 2012-09-12
WO2011076619A1 (fr) 2011-06-30
FR2954332B1 (fr) 2012-01-13
EA022744B1 (ru) 2016-02-29
JP5702803B2 (ja) 2015-04-15

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